Naphtholactam dyes

ABSTRACT

The invention concerns naphtholactam derivatives of formula (I), in which: R 1  represents hydrogen, optionally substituted C 1  -C 6  alkyl C 5  -C 6  cycloalkcyl or substituted phenyl; R 2  and R 3  represent hydrogen, C 1  -C 8  alkanoyl, optionally substituted benzoyl, optionally substituted C 2  -C 4  alkyl, optionally substituted C 2  -C 4  alkenyl, optionally substituted C 2  -C 4  alkinyl, a halogen, nitro, sulphamoyl, optionally substituted hydroxy, optionally substituted mercapto, C 1  -C 6  alkysulphonyl or optionally substituted phenylsulphonyl; R 4  represents hydrogen or, with R 3 , a group of formula (II); R 5  represents hydrogen or C 1  -C 6  alkyl; R 6  represents cyano, carbamoyl, C 1  -C 4  mono- or dialkylcarbamoyl carboxyl or C 1  -C 4  alkoxycarbonyl; and R 7  represents substituted C 1  -C 4  alkyl, optionally substituted C 5  -C 13  alkyl or benzoyl. Also disclosed is the use of these derivatives for dyeing or printing textiles.

CROSS REFERENCE

This application is a 371 of PCT/UEP 95/03112 filed Aug. 4, 1995.

The present invention relates to novel naphtholactam derivatives of theformula I ##STR2## where R¹ is hydrogen, substituted or unsubstituted C₁-C₆ -alkyl, C₅ -C₇ -cycloalkyl or substituted or unsubstituted phenyl,

R2 and R³ are independently of each other hydrogen, C₁ -C₈ -alkanoyl,substituted or unsubstituted benzoyl, substituted or unsubstituted C₂-C₄ -alkyl, substituted or unsubstituted C₂ -C4-alkenyl, substituted orunsubstituted C₂ -C₄ -alkynyl, nitro, sulf amoyl hydroxyl, mercapto, C₁-C₆ -alkoxy, substituted or unsubstituted phenoxy, C₁ -C₆ -alkylthio,substituted or unsubstituted phanylthio, C₁ -C₆ -alkylsulfonyl orsubstituted or unsubstituted phenylsulfonyl,

R⁴ is hydrogen or together with R³ a radical of the formula ##STR3## R⁵is hydrogen, R⁶ is cyano, carbamoyl, mono- or di(C₁ -C₄-alkyl)carbamoyl, carboxyl or C₁ -C₄ -alkoxycarbonyl, and

R⁷ is substituted or unsubstituted C₅ -C₁₃ -alkyl with or withoutinterruption by from 1 to 3 oxygen atoms in ether function, by from 1 to3 sulfur atoms or by from 1 to 3 imino or C₁ -C₄ -alkylimino groups, oris benzoyl,

and to their use for dyeing or printing textile materials.

DE-A-2 611 6685 (≈FR-A-2 344 603) and U.S. Pat. No. 4,096,145 disclosedyes based on similar naphtholactam derivatives. However, it has beenfound that the products described therein have application defects.

DE-A-2 705 108 and Chem. Abstr. 99 1983, 24028k, also describenaphtholactam dyes.

It is an object of the present invention to provide novel naphtholactamdyes which show advantageous application properties. More particularly,the novel dyes shall possess high color strength and brilliance and havegood in-use/service properties.

We have found that this object is achieved by the above-definednaphtholactam derivatives of the formula I.

Any alkyl or alkenyl appearing in the abovementioned formulae may bestraight-chain or branched.

Any substituted alkyl appearing in the abovementioned formulae may haveas substituents for example cyclohexyl, phenyl, C₁ -C₄ -alkylphenyl, C₁-C₄ -alkoxyphenyl, halophenyle C₁ -C₁₃ -alkanoyloxy, C₁ -C₁₃-alkoxycarbonyl, C₁ -C₁₃ -alkoxycarbonyloxy, the alkyl chain of thethree all sic! last-mentioned radicals being optionally interrupted byfrom 1 to 3 oxygen atoms in ether function and/or phenyl- orphenoxy-substituted, cyclohexyloxy, phenoxy, halogen, hydroxyl or cyano.The number of substituents in substituted alkyl is generally 1 or 2.

Any interrupted alkyl appearing in the abovementioned formulae ispreferably interrupted, unless otherwise stated, by 1 or 2 oxygen atomsin ether function, sulfur atoms or imino or C₁ -C₄ -alkylimino groups.

Any substituted phenyl appearing in the abovementioned formulae may haveas substituents for example, unless otherwise stated, C₁ -C₈ -alkyl, C₁-C₈ -alkoxy, nitro or halogen, especially chlorine or bromine. Thenumber of substituents in substituted phenyl is generally from 1 to 3.

Any substituted alkenyl appearing in the abovementioned formula I mayhave as substituents for example phenyl, C₁ -C₁₃ -alkoxy-carbonyla cyanoor hydroxyl. The number of substituents in substituted alkenyl isgenerally one.

Any substituted alkynyl appearing in the abovementioned formula I mayhave as substituents for example hydroxyl, phenyl, C₁ -C₁₃-alkoxycarbonyl or cyano. The number of substituents in substitutedalkynyl is generally one.

R¹ and R⁵ are each for example methyl or else--and this also applies toR² and R³ --ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl ortert-butyl.

R¹ and R⁵ may each also be for example--and this also applies to R⁷--pentyl, isopentyl, neopentyl, tert-pentyl, hexyl or 2-methylpentyl.

R⁷ may also be for example heptyle 1-ethylpentyl, octyl, 2-ethylhexyl,isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl,isotridecyl (the above designations isooctyl, isononyl, isodecyl andisotridecyl are trivial names derived from the oxo process alcohols--cf.Ullann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol, A1,pages 290 to 293, and also Vol. A 10, pages 284 and 285),2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- or 3-ethoxypropyl,2- or 3-propoxypropyl, 2- or 3-butoxypropyl, 2- or 4-methoxybutyl, 2- or4-thoxybutyl, 2- or 4propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl,4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7dioxanonyl, 4,7dioxaoctyl,4,7-dioxanonyl, 2- or 4-butoxybutyl, 4,8-dioxadecyl, 3,6,9-trioxadecyl,3,6,9-trioxaundecyl, 3,6,9-trioxadodecyl, 4,11-dioxapentadecyl,6-phenoxy-4-oxahexyl, 3-phenoxy-4-oxahexyl, 2- or 3-ethylthiopropyl, 2-or 4-methyithiobutyl, 2- or 4-ethylthiobutyl, 2-dimethylaminopropyl,4-aza-4-methylpentyl, 2-ethylaminopropyl, 4-azahexyl,2-diethylaminopropyl, 4-aza-4-ethylhexyl, 5-azahexyl,5-aza-5-methylhexyl, 5-azaheptyl, 5-aza-5-ethylheptyl, 3,6-diazaheptyl,3,6-diaza-6-methylheptyl or 3,6-diaza-3,6-dimethylheptyl.

R¹, R2 and R³ may each also be 2-methoxycarbonylethyl,2-ethoxycarbonylethyl, 2- or 3-methoxycarbonylpropyl, 2- or3-ethoxycarbonylpropyl, 2- or 3-butoxycarbonylpropyl,4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl,2-methoxycarbonyloxyethyl, 2-ethoxycarbonyloxyethyl, 2- or3-methoxycarbonyloxypropyl, 2- or 3-ethoxycarbonyloxypropyl, 2- or4-methoxycarbonyloxybutyl, 2- or 4-ethoxycarbonyloxybutyl, 2-cyanoethyl,2- or 3-cyanopropyl, 4-cyanobutyl, 2-acetyloxyethyl,2-propionyloxyethyl, 2- or 3-acetyloxypropyl, 2-hydroxyethyl, 2- or3-hydroxypropyl, 4-hydroxybutyl, 2-cyclohexyloxyethyl, 2- or3-cyclohexyloxypropyl, 2- or 4-cyclohexyloxybutyl, phenoxymethyl,2-phenoxyethyl, 2- or 3-phenoxypropyl, 2- or 4-phenoxybutyl,2-cyclohexylethyl, 2- or 3-cyclohexylpropyl or benzyl, 1- or2-phenylethyl, 2-chloroethyl, 2- or 3-chloropropyl or 2- or4-chlorobutyl.

R¹ may also be for example cyclopentyl, cyclohexyl, cycloheptyl, phenyl,2-, 3- or 4methylphenyl, 2,4-dimethylphenyl, 2-, 3- or 4-methoxyphenyl,2,4-dimethoxyphenyl, 2-, 3- or 4-chlorophenyl or 2,6-dichlorophenyl.

R² and R³ may each also be for example formyl, acetyl, propionyl,butyryl, isobutyryl, pentanoyl, isopentanoyl, hexanoyl, heptanoyl,octanoyl, 2-ethylhexanoyl, benzoyl, 2-, 3- or 4-methylbenzoyl, 2-, 3- or4-methoxybenzoyl, 2-, 3- or 4-chlorobenzoyl, allyl, methallyl, styryl,2-methoxycarbonylprop-1-en-1-yl, 2-ethoxycarbonylpropl1-en-1-yl,2-(2-ethylhexyloxycarbonyl) prop-1-en-1-yl,2-tridecyloxycarbonylprop1-en-1-yl,2-isotridecyloxycarbonylprop-1-en-1-yl, ethynyl, prop-1-yn-1-yl,prop-1-yn-3-yl, 3-hydroxyprop-1-yn-1-yl, but-1-yn-1-yl, but-2-yn-1-yl,methylthio, ethylthio, propylthio, isopropylthio, butylthio,isobutylthio, pentylthio, hexylthio, phenylthio, 2-methylphenylthio,2-methoxyphenylthio, 2-chlorophenylthio, methoxy, ethoxy, propoxy,isopropoxy, butoxy, isobutoxy, sec-butoxy, pentyloxy, isopentyloxy,neopentyloxy, tert-entyloxy, hexyloxy, 2-methylpentyloxy, phenoxy, 2-,3- or 4-methylphenoxy, 2-, 3- or 4-methoxyphenoxy, methylsulfonyl,ethylsulfonyl, propylsulfonyl, isopropylsulgonyl, butylsulfonyl,isobutylsulfonyl sec-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl,neopentylsulfonyl, hexylsulfonyl, phenylsulfonyl,2-methylphenylsulfonyl, 2-methoxyphenylsulfonyl or2-chlorophenylsulfonyl.

R⁶ is for example methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl,isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl,sec-butoxycarbonyl, mono- or dimethylcarbamoyl, mono- ordiethylcarbamoyl, mono- or dipropylcarbamoyl, mono- ordiisopropylcarbamoyl, mono- or dibutyloarbamoyl orN-methyl-N-ethylcarbamoyl.

Preference is given to naphtholactam derivatives of the formula I whereR¹ is hydrogen.

Preference is further given to naphtholactam derivatives of the formulaI where R² is hydrogen,

Preference is further given to naphtholactam derivatives of the formulaI where R³ is hydrogen, C₂ -C₄ -alkanoyl, benzoyl, halogen, nitro, C₁-C₆ -alkylthio, phenylthio or together with R⁴ a radical of the formula##STR4##

Preference is further given to naphtholactam derivatives of the formulaI where R⁵ is hydrogen or methyl, especially hydrogen.

Preference is further given to naphtholactam derivatives of the formulaI where R⁶ is cyano.

Preference is further given to naphtholactam derivatives of the formulaI where R⁷ is C₅ -C₁₃ -alkyl with or without substitution by phenoxy andwith or without interruption by from 1 to 3 oxygen atoms in etherfunction, or is phenylethyl.

Particular preference is given to naphtholactam dyes of the formula Iwhere R⁷ is C₆ -C₁₃ -alkyl, especially C₇ -C₁₃ -alkyl, C₅ -C₁₃ -alkylwhich is interrupted by 1 or 2 oxygen atoms in ether function, orphenylethyl.

Particular preference is further given to naphtholactam derivatives ofthe formula Ia ##STR5## where X¹ is hydrogen, C₂ -C₄ -alkanoyl, benzoyl,nitro, C_(1-C) ₆ -alkylthio or phenylthio,

X² is hydrogen or together with X¹ a radical of the formula ##STR6## X³is C₅ -C₁₃ -alkyl with or without substitution by phenoxy and with orwithout interruption by from 1 to 3 oxygen atoms in ether function, oris phenylethyl.

The naphtholactam derivatives of the formula I according to the presentinvention can be obtained by conventional methods.

For example, a naphtholactam of the formula IIa or IIb ##STR7## where Z¹is oxygen or sulfur, Z² is C₁ -C₄ -alkyl and An⊖ is the equivalent of ananion (e.g. halide, methosulfate or ethosulfate) and R¹, R², R³ and R⁴are each as defined above, can be condensed with a pyridone of theformula III ##STR8## where R⁵, R⁶ and R⁷ are each as defined above.

A condensing agent is required in the case of Z¹ oxygen, but not in thecase of compounds where Z¹ is sulfur or which conform to the formula Ib.

Examples of suitable condensing agents include phosphorus halides, suchas phosphorus pentachloride, phosphorus trichloride, phosphorusoxychloride or phosphorus oxybromide. The use of phosphorus oxychlorideis preferred.

The reaction can be carried out in a diluent, for example a glycolether, such as methylglycol, ethylglycol, methyldiglycol orethyldiglycol, γ-butyrolactone, dichloroethane, chlorobenzene,dichlorobenzene, nitrobenzene or dioxane, or else in an excess ofcondensing agent,

If the reaction of the naphtholactams is carried out without acondensing agent, the abovementioned diluents are likewise alsosuitable, but in addition there may be mentioned for example pyridine,N,N-dimethylformamide or N-methylpyrrolidone.

The naphtholactam derivatives of the formula I according to the presentinvention are advantageously useful for dyeing or printing textilematerials These exhibit for example fibers or fabrics made of celluloseesters or polyesters but also of polyamides, or blends of polyesters andcellulose fibers. The dyeings or prints obtained have a high fastness todry heat setting and pleating, a high color strength and a highbrilliance and also good in-use/service fastness properties.

To obtain a favorable color build-up, it can be of advantage in somecases to dye with mixtures between the naphtholactam derivatives of theformula I.

The naphtholactam derivatives of the present invention are alsoadvantageously useful for thermal transfer from a transfer toplastic-coated paper by means of an energy source (see e.g. EP-A-416434).

The Examples which follow illustrate the invention.

EXAMPLE 1

8.2 ml (0.09 mol) of phosphoryl chloride were added dropwise withstirring at 80° C. to a mixture of 150 ml of γ-butyrolactone, 8.2 g(0.03 mol) of 4-benzoylnaphtholactam and 7.3 g (0.037 mol) of1-(4-oxahexyl)-3-cyano-6-hydroxypyrid-2-one. The reaction mixture wasstirred at 120° C. for 6 h and then distilled at 0.5-0.7 mbar and 50-54°C. to remove γ-butyrclactone and phosphorus oxychloride, 70 ml ofethanol were then gradually added dropwise at the same temperature withstirring, and the mixture was cooled down to room temperature andstirred at room temperature for 2 h. The dye was then filtered off,washed with petroleum ether and dried to leave 7.5 g (54%) of the dye ofthe formula ##STR9## in the form of red crystals.

(mp.: 128-135° C.; λ_(max) : 278 nm, 548 nm, in CH₂ Cl₂)

EXAMPLE 2

a) 5 g (0.02 mol) of 4-bromonaphtholactam, 2.3 g (0.022 mol) of styrene,3.9 g (0.21 mol) of tributylamine, 0.052 g (0.0002 mol) oftriphenylphosphine and 0.0022 g (0.00001 mol) of palladium acetate werecombined under nitrogen and heated to 150° C. for 4 h with stirring. Themixture was then cooled down to room temperature and dissolved in 1200ml of acetone with heating, and the catalyst was filtered off. Thesolution was then slowly concentrated at room temperature, obtaining4.16 g (77%) of crystals of a yellow product of the formula ##STR10## b)1.48 g of the compound obtained under a) were condensed with 1.47 g of1-hexyl-3-cyano-6-hydroxypyrid-2-one by the method of Example 2,affording 2.34 g (90%) of the compound of the formula ##STR11## (λ_(max): 558 nm, in CH₂ Cl₂)

EXAMPLE 3

8.4 g (0.05 mol) of naphtholactam and 11.6 g (0.05 mol) of1-heptyl-3-cyano-6-hydroxypyrid-2-one were stirred at 50° C. in 35 ml of1,2-dichloroethane for 15 min. Thereafter 10 ml of phosphorusoxychloride were added dropwise, and stirring was continued for afurther 2 h at 80° C. Thereafter excess phosphorus oxychloride wasdischarged at room temperature, which also brought down the product. Themixture was subsequently stirred overnight at room temperature andfiltered with suction, and the filter residue was washed with methanol,leaving 8.71 g (45.2%) of a product of the formula ##STR12## (mp.: 212°C.;λ_(max) : 507 nm, 544 nm, in CH₂ Cl₂)

The same method can be used to obtain the naphtholactam derivativeslisted below: ##STR13##

    __________________________________________________________________________                                    λ.sub.max    Ex.                             (CH.sub.2 Cl.sub.2)                                         Hue on    No.       Z.sup.1         Z.sup.2     Z.sup.3   mp.  ° C.!                                     nm! polyester    __________________________________________________________________________     3 H COC.sub.6 H.sub.5                     C.sub.6 H.sub.13                               >230 510, red                                    550     4 H SC.sub.6 H.sub.5                     C.sub.6 H.sub.13                               199-205                                    518  violet                                    556     5 H COC.sub.3 H.sub.7                     C.sub.6 H.sub.13                               158-166                                    510, red                                    548     6 H COC.sub.6 H.sub.5                     CH.sub.2 (C.sub.2 H.sub.5)C.sub.4 H.sub.9                               102-156                                    510  red                                    550     7 H COC.sub.3 H.sub.7                     C.sub.3 H.sub.6 OC.sub.2 H.sub.5                               120-145                                    360, red                                    548     8 H NO.sub.2    CH.sub.2 (C.sub.2 H.sub.5)C.sub.4 H.sub.9                               >230 556  violet     9 H COC.sub.3 H.sub.7                     CH.sub.2 (C.sub.2 H.sub.5)C.sub.4 H.sub.9                               168-177                                    510, red                                    548    10 H SO.sub.2 CH.sub.3                     CH.sub.2 (C.sub.2 H.sub.5)C.sub.4 H.sub.9                               190-204                                    520, red                                    560    11 H NO.sub.2    C.sub.6 H.sub.13                                    518, red                                    556    12 H SO.sub.2 CH.sub.3                     C.sub.6 H.sub.13                                    518, red                                    558    13 H C.tbd.CC(CH.sub.3).sub.2 OH                     C.sub.6 H.sub.13                                    570  violet    14 H CH═C(CH.sub.3)COOC.sub.13 H.sub.27                     C.sub.6 H.sub.13                                    564  red    15 H H           (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6 H.sub.5                               136  507,                                    544    16 H H           CH.sub.2 (C.sub.2 H.sub.5)C.sub.4 H.sub.9                               181-194                                    506,                                    544    17 H H           C.sub.6 H.sub.13                               218  507,                                    544    18 H H           CH.sub.2 C(CH.sub.3).sub.3                                    523, red                                    557    19 H H           C.sub.2 H.sub.4 (C.sub.2 H.sub.5)C.sub.4 H.sub.9                                         red    20       1       (mp.: 250° C.; λ.sub.max : 515 nm, in N,N-Dimethylformami       de)    21       2 #STR14##       (mp.: 618 nm, 672 nm, in CH.sub.2 Cl.sub.2)    __________________________________________________________________________

We claim:
 1. An naphtholactam derivative of the formula I ##STR15##where R¹ is hydrogen, substituted or unsubstituted C₁ -C₆ -alkyl, C₅ -C₇-cycloalkyl or substituted or unsubstituted phenyl,R² and R³ areindependently of each other hydrogen, C₁ -C₈ -alkanoyl, substituted orunsubstituted benzoyl, substituted or unsubstituted C₂ -C₄ -alkyl,substituted or unsubstituted C₂ -C₄ -alkenyl, substituted orunsubstituted C₂ -C₄ -alkynyl, nitro, sulfamoyl, hydroxyl, mercapto, C₁-C₆ -alkoxy, substituted or unsubstituted phenoxy, C₁ -C₆ -alkylthio,substituted or unsubstituted phenylthio, C₁ -C₆ -alkylsulfonyl orsubstituted or unsubstituted phenylsulfonyl, with the proviso that oneof R² and R³ is other than hydrogen, R⁴ is hydrogen or together with R³a radical of the formula ##STR16## R⁵ is hydrogen, R⁶ is cyano,carbamoyl, mono- or di(C₁ -C₄ -alkyl)carbamoyl, carboxyl or C₁ -C₄-alkoxycarbonyl, and R⁷ is substituted or unsubstituted C₅ -C₁₃ -alkylwith or without interruption by from 1 to 3 oxygen atoms in etherfunction, by from 1 to 3 sulfur atoms or by from 1 to 3 imino or C₁ -C₄-alkylimino groups, or is benzoyl.
 2. A naphtholactam derivative asclaimed in claim 1 wherein R¹ is hydrogen.
 3. A naphtholactam derivativeas claimed in claim 1 wherein R² is hydrogen.
 4. A naphtholactamderivative as claimed in claim 1 wherein R³ is hydrogen C₂ -C₄-alkanoyl, benzoyl, nitro, C₁ -C₆ -alkylthio, phenylthio or togetherwith R⁴ a radical of the formula ##STR17##
 5. A naphtholactam derivativeas claimed in claim 1 wherein R⁵ is hydrogen or methyl.
 6. Anaphtholactam derivative as claimed in claim 1 wherein R⁶ is cyano.
 7. Anaphtholactam derivative as claimed in claim 1 wherein R7 is C₅ -C₁₃-alkyl with or without substitution by phenoxy and with or withoutinterruption by from 1 to 3 oxygen atoms in ether function, or isphenylethyl.
 8. A naphtholactam derivative as claimed in claim 1 whereinR⁷ is C₆ -C₁₃ -alkyl, C₅ -C₁₃ -alkyl which is interrupted by 1 or 2oxygen atoms in ether function, or phenylethyl.
 9. A naphtholactamderivative as claimed in claim 1 of the formula Ia whereX¹ is, C₂ -C₄-alkanoyl, benzoyl, nitro, C₁ -C₆ -alkylthio or phenylthio, X² ishydrogen or together with X¹ a radical of the formula ##STR18## X³ is C₅-C₁₃ -alkyl with or without substitution by phenoxy and with or withoutinterruption by from 1 to 3 oxygen atoms in ether function, or isphenylethyl.
 10. A method comprising dyeing or printing textilematerials with a naphtholactam derivative of claim
 1. 11. Thenaphtholactam derivatives of Claim 1, having the following formula:##STR19##